EP2406620B1 - Vorrichtung zur bereitstellung einer vorrichtung zur internen kalibrierung bei einem elektrochemischen sensor - Google Patents

Vorrichtung zur bereitstellung einer vorrichtung zur internen kalibrierung bei einem elektrochemischen sensor Download PDF

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EP2406620B1
EP2406620B1 EP10751364.0A EP10751364A EP2406620B1 EP 2406620 B1 EP2406620 B1 EP 2406620B1 EP 10751364 A EP10751364 A EP 10751364A EP 2406620 B1 EP2406620 B1 EP 2406620B1
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aie
analyte
electrolytic layer
conductive
electrolytic
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French (fr)
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EP2406620A1 (de
EP2406620A4 (de
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Joseph A. Duimstra
Lee Leonard
Gregory G. Wildgoose
Eric Lee
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Parker Hannifin Corp
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Parker Hannifin Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/36—Glass electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs

Definitions

  • the present invention provides methods and devices for measuring the concentration of an analyte in solution and relates to the field of chemistry.
  • the reference electrode is usually a chloridized silver (Ag
  • KCl potassium chloride
  • the system is maintained at equilibrium and the potential drop (i.e. the measured voltage) across the electrode-electrolyte interface of the conventional reference electrode is then thermodynamically fixed and constant.
  • the function of the reference electrode is then to provide a fixed potential to which other measurements, such as pH, may be compared.
  • a remarkable advance in pH sensor technology is the solid state internally calibrated pH sensor comprised of two redox-active pH sensitive agents (anthraquinone (AQ) and 9,10-phenanthrenequinone (PAQ)) and one pH insensitive redox agent (e.g., Ferrocene (Fc)); see PCT Patent Publication Nos. 2005/066618 and 2007/034131 and GB Patent Publication No. 2409902 .
  • all three redox agents may be mixed together with multiwalled carbon nanotubes (MWCNT), graphite powder and epoxy, and the resulting admixture cured and formed into solid sensors.
  • the pH insensitive peak (due to Fc) should ideally be constant and independent of pH or ionic species in solution and should not drift over time.
  • the AQ and PAQ peaks should ideally vary their position on the voltage sweep in a predictable fashion depending on the pH of the solution being measured.
  • the positions of the pH sensitive peaks when compared to the position of the pH insensitive peak, allow the solution pH to be deduced by comparing those values to a calibration table.
  • the pH insensitive peak must be stable over time, and its peak position must be unaffected by varying solution compositions. Otherwise, the accuracy of the system is compromised.
  • the present invention meets this need.
  • analyte insensitive material (AIM)
  • AIM analyte insensitive material
  • an electrolytic layer which can be composed of, for example and without limitation, room temperature ionic liquids (RTIL) or other ionic liquids or liquids with sufficient ionic strength, can be used to achieve the desired results when used as a salt bridge between the AIM and the sample being analyzed; and (iii) with such an electrolytic layer, an analyte sensitive material (ASM) can be used in place of or in addition to an AIM, because the ASM is converted functionally into an AIM when a suitable electrolytic layer is employed.
  • RTIL room temperature ionic liquids
  • ASM analyte sensitive material
  • the electrolytic layer (e.g. composed of an RTIL or other suitable material, as described herein) provides the constant chemical environment and ionic strength for the AIM (or ASM) and provides a layer that limits or eliminates direct chemical interaction with the sample being analyzed.
  • a broad range of redox active materials can be employed in a variety of configurations in accordance with the methods and in the "analyte insensitive electrodes" (AIEs) of this invention and devices containing them.
  • the present invention provides a variety of AIEs for use in the internally calibrated pH and other analyte sensors based on redox agents provided by the invention.
  • the schematic shown in Figure 2 provides illustrative embodiments of this aspect of the invention.
  • the oval dots represent the redox active material.
  • the electrolytic layer e.g. RTIL or other material
  • the electrolytic layer is in a porous structure or "conductive physical barrier", which serves to limit direct chemical interaction and enhance electronic communication between the sample test solution and the redox active material.
  • redox active materials e.g. AIMs or ASMs
  • AIMs e.g. AIMs or ASMs
  • redox active materials that have been tested and demonstrated to be useful in the methods and devices of the invention are shown in Figure 3 .
  • the invention relates to compositions, devices, electrodes, sensors, systems, and methods useful for detecting the presence of an analyte or measuring the analyte concentration in a sample.
  • the invention provides a means of continuous internal self-calibration for such measurements.
  • the invention provides a substantially analyte insensitive electrode (AIE), and in one embodiment, this electrode employs a substantially analyte insensitive redox active material (AIM) to generate a predictable analyte insensitive signal, while in another embodiment, this electrode employs a substantially analyte sensitive redox active material (ASM) to generate a predictable analyte insensitive signal.
  • AIE substantially analyte insensitive electrode
  • AIM substantially analyte insensitive redox active material
  • ASM substantially analyte sensitive redox active material
  • the invention provides a voltammetric or amperometric analyte sensor system in which an AIE of the invention generates a signal that is compared with an analyte sensitive signal from an analyte sensitive electrode (ASE) to provide a means for continuous internal self-calibration.
  • AIE of the invention generates a signal that is compared with an analyte sensitive signal from an analyte sensitive electrode (ASE) to provide a means for continuous internal self-calibration.
  • the present invention thus meets the need for an AIE capable of generating a substantially analyte insensitive signal in response to the application of an electrical stimulus applied to the sample being analyzed in the course of making voltammetric or amperometric measurements of analyte concentration in the sample.
  • the electrodes of the invention provide a predictable signal useful as an internal standard (in other words, a standard internal to the system) with which an analyte sensitive signal may be continuously compared, and therefore permit greater accuracy and reproducibility in determining analyte concentration.
  • the present invention therefore provides an AIE that can be used in an electrochemical analyte sensing device that is capable of generating a substantially analyte-insensitive electrical response when an electrical stimulus is applied to an analyte sample in the course of making voltammetric and/or amperometric measurements of analyte concentration.
  • the invention also provides a self-calibrating electrochemical analyte sensor system which incorporates such an electrode.
  • the invention also provides a method of using such an electrode as an internal self-calibrating standard in an analyte sensor system, e.g. for the purpose of making voltammetric and/or amperometric measurements to determine the presence and/or concentration of an analyte in a sample.
  • the invention also provides a method of making such an AIE.
  • the invention also provides a multi-phase AIE for use in an electrochemical sensing device for measuring an analyte in a sample, comprising: (a) a first phase comprising an electrolytic layer (which can be, for example and without limitation, an ionic liquid (IL), which in one embodiment is a liquid comprised solely of ions, wherein the IL phase is adjacent to the sample and substantially immiscible with the sample), (b) an electrically conductive component electrically connected to the electrolytic layer, and (c) a redox active material (RAM), capable of being electrochemically oxidized and/or electrochemically reduced, wherein the redox activity of the redox active material is substantially insensitive to the analyte, and wherein further the redox active material may be dispersed in either the electrolytic layer or the conductive component.
  • an electrolytic layer which can be, for example and without limitation, an ionic liquid (IL), which in one embodiment is a liquid comprised solely of ions, wherein the IL phase
  • the electrolytic layer is an IL, such as a room temperature IL (RTIL), i.e. a liquid comprised entirely of ions which is liquid at temperatures below 100 degrees Celsius.
  • RTIL room temperature IL
  • the RTIL is N-butyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide (C4mpyrrNTf2).
  • the analyte is dispersed in a liquid sample, and/or is an ion dispersed in a liquid sample, and/or is hydrogen ion.
  • the analyte is a non-ionic species dispersed in a liquid species.
  • the redox active material in the AIE is selected from the group consisting of redox-active organic molecules, redox-active polymers, metal complexes, organometallic species, metals, metal salts, or semiconductors, and undergoes one or more electron transfer processes not involving any reaction or chemical interaction with the target analyte.
  • the redox active material in the AIE is n-butyl-ferrocene.
  • the redox active material in the AIE is K 4 Fe(CN) 6 .
  • the conductive component comprises an electrically conductive material selected from the group consisting of carbon allotropes and derivatives thereof, transition metals and derivatives thereof, post-transition metals and derivatives thereof, conductive metal alloys and derivatives thereof, silicon and derivatives thereof, conductive polymeric compounds and derivatives thereof, and semiconductor materials and derivatives thereof.
  • the conductive component further comprises a composite material comprising a binder and an electrically conductive material.
  • the electrically conductive material present in the composite material comprises graphite and/or glassy carbon, and/or multi-walled carbon nanotubes (MWCNTs) and/or single-walled carbon nanotubes (SWCNTs), and/or any combination thereof.
  • the composite material further comprises a redox active material.
  • the redox active material is n-butyl-ferrocene.
  • the composite material comprises a redox-active ASM with conferred analyte insensitivity as a consequence of the AIE construct.
  • the AIE further comprises a conductive physical barrier adjacent to the sample, for physically separating the electrolytic layer (e.g. IL phase) from the sample.
  • the conductive physical barrier is selectively impermeable to the analyte.
  • the conductive physical barrier is selectively permeable or selectively impermeable to non-analyte species in the sample.
  • the conductive physical barrier is a porous frit.
  • the conductive physical barrier is a membrane.
  • the conductive physical barrier is a film.
  • the AIE further comprises a second electrolytic layer adjacent to the first electrolytic layer interposed between the conductive component and the first electrolytic layer and in electrical connection with the conductive component and the first electrolytic layer, and a conductive physical barrier layer interposed between the first and second electrolytic layers, for physically separating the electrolytic layers from each other, wherein, optionally, the first electrolytic layer is substantially immiscible with the second electrolytic layer and wherein further the redox active material may also be dispersed in the second electrolytic layer.
  • the second electrolytic layer is selected from the group consisting of an aqueous electrolyte solution, a gelled aqueous electrolyte solution, an electrolytic sol gel, and an organic electrolyte solution.
  • the present invention further provides an electrochemical sensing device for measuring an analyte in a sample, comprising (a) an AIE as described above in any of its various embodiments, and (b) a working electrode in electrical connection with the AIE, and comprising a redox-active analyte sensitive material (ASM), capable of being electrically oxidized and/or electrically reduced, and wherein the redox activity of the ASM is substantially sensitive to the analyte.
  • Working electrodes suitable for use in the sensing devices of the invention include, for example and without limitation, those described in provisional U.S. patent application Serial Nos. 61/161,139 , filed 25 Mar 09; 61/225,855 , filed 15 Jul 09; and 61/289,318 , filed 22 Dec 09.
  • the AIE and the working electrode are in parallel electrical connection. In other embodiments, the AIE and the working electrode are configurationally joined and electrically connected by a common conducting component. In another embodiment, the AIE and the working electrode are electrically connected within a single-channel electronic controlling device. In some embodiments, the AIE and the working electrode are connected on separate data channels within a multi-channel electronic controlling device.
  • the electrochemical sensing device of the present invention further comprises an electronic device for generating and/or measuring an analytical signal. In another embodiment, the electrochemical sensing device of the present invention further comprises a conventional reference electrode or a pseudo-reference electrode.
  • the present invention further provides a method of using the sensing device of the present invention for measuring an analyte in a sample, comprising the steps of applying an electrical signal to the AIE, and measuring the electrical response of the AIE, wherein the electrical response of the AIE is independent of analyte concentration in the sample.
  • the measured electrical response of the AIE remains substantially constant over time and repeated use.
  • the measured electrical response of the AIE varies in a substantially predictable manner over time and repeated use.
  • the measured electrical response of the AIE remains substantially constant relative to a reference potential, independent of the analyte, upon application of the electrical signal to the AIE.
  • the measured electrical response of the AIE varies in a substantially predictable manner relative to a reference potential, independent of the analyte, upon application of the electrical signal to the AIE. In some embodiments, the measured electrical response of the AIE remains substantially constant relative to a known electrical response. In another embodiment, the measured electrical response of the AIE varies in a substantially predictable manner relative to a known electrical response.
  • an “analyte” is a chemical species of interest present in a sample, the presence of which is detectable or the concentration of which is measurable by using an analyte sensor system which incorporates the AIE of the present invention as a self-calibrating internal standard that provides either a substantially constant or a predictable response during analyte sensing. "Substantially constant” is used to mean constant within a range defined by the end user.
  • RAM redox active material
  • Redox activity refers to either or both of those processes.
  • an “analyte insensitive material” also known as a “chemically insensitive redox active material” is a redox active material that is insensitive, or substantially insensitive, to the presence or the concentration of an analyte in a sample.
  • “Substantially insensitive” to an analyte is used to mean insensitive within the tolerances required for a given application, as those tolerances are defined by an end user.
  • ASM is a redox active material that (when not in an AIE of the invention) is sensitive or substantially sensitive to the presence or concentration of an analyte in a sample within those user-defined application-specific tolerances.
  • an ASM is functionally equivalent to an AIM when utilized in an AIE of the invention.
  • any reference to an AIM should be considered to be a reference to an ASM (or AIM) in connection with a description of a redox active material for use in an AIE of the invention.
  • the term RAM may be used to indicate that any redox active material (i.e. an AIE or an ASM) can be employed.
  • a RAM to be "dispersed" means that it is dissolved in a solution or colloidally suspended in a gas, liquid or solid.
  • the term is also intended to encompass embodiments wherein the RAM is abrasively immobilized, adsorbed, electrostatically bound or covalently bound to the surface of a solid or to a component of the solid.
  • the term is also intended to encompass embodiments wherein the RAM is incorporated as a dopant in a crystal lattice.
  • the term is also intended to encompass an intercalation of the RAM within a solid.
  • the RAM is dispersed in a membrane that serves as a conductive physical barrier.
  • An “electrochemical sensing system” is a system of electrodes which is capable of measuring the presence and/or concentration of an analyte in a sample.
  • Such systems generally include a working electrode, a reference electrode (either a conventional or pseudo reference electrode) and a counter electrode.
  • the system may include only a reference electrode and working electrode.
  • the system may include a controller/processor device.
  • a “working electrode” is the electrode at which the electrochemical process of interest occurs.
  • the working electrode may be sensitive to one or more analyte(s) in the test solution, or it may be chemically modified with analyte sensitive species/materials.
  • the electrochemical response of the working electrode is measured after some perturbation has been applied to the system under study.
  • the perturbation may be the application of a potential difference to the WE which induces electron transfer to occur, and the resulting current at the working electrode is then recorded as a function of either the applied potential (voltammetric mode) or time (chronoamperometric mode).
  • An “analyte insensitive electrode” is a special case of a working electrode where the current flow depends in part on redox processes that are independent of the presence or concentration of species (apart from a minimum threshold of supporting electrolyte) in the sample composition including but not limited to the analyte. AlEs of the invention are described in more detail below.
  • RE reference electrode
  • CREs Conventional reference electrodes
  • a CRE typically comprises two halves of a redox couple in contact with an electrolyte of fixed ionic composition and ionic strength. Because both halves of the redox couple are present and the composition of all the species involved is fixed, the system is maintained at equilibrium, and the potential drop (i.e. the measured voltage) across the electrode-electrolyte interface of the CRE is then thermodynamically fixed and constant.
  • a commonly used CRE system is the Ag
  • the two half-cell reactions are therefore: Ag + + e - ⁇ Ag; and AgCl + e - ⁇ Ag + Cl - .
  • two-electrode configurations can be used in the special case where the WE is a microelectrode, having at least one dimension typically smaller than 100 microns.
  • the currents passed at the WE are small, and therefore a two-electrode cell can be used with a CRE, but without the need for a CE.
  • PRE palladium-reference electrode
  • a type of reference electrode which is sometimes used, particularly in non-aqueous electrolytes. These electrodes typically do not comprise both halves of a well-defined redox potential and are therefore not thermodynamic reference electrodes of fixed composition and potential. However, they provide a reasonably constant potential over the timescale of an electrochemical experiment (on the order of minutes), and the absolute potential of the PRE can then be calibrated back to a CRE if required.
  • a PRE is a silver wire (used commonly in non-aqueous electrochemistry).
  • CE counter electrode
  • auxiliary electrode This electrode simply serves as a source or sink of electrons and allows current to flow through the cell.
  • CEs are typically made using relatively chemically inert materials, commonly Pt, but carbon (graphite) is also commonly employed.
  • a “conductive physical barrier” is a layer that is either adjacent to the sample being analyzed or is interposed between two adjacent phases of the AIE.
  • a conductive physical barrier is "selectively impermeable" to a species in a sample when it prevents the species from passing through it but allows other components of the sample, such as charge carriers in the electrolyte component of the sample, to do so freely.
  • a conductive physical barrier is "selectively permeable” to a species in the sample when it allows the species to move freely across it.
  • the AIE may incorporate more than one conductive physical barrier as a means of physically separating the various components of the AIE from one another as well as from the sample being analyzed.
  • an “ionic liquid” is a liquid comprised principally of both cations and anions.
  • an “ionic liquid” is a liquid comprised entirely of both cations and anions.
  • a “room temperature ionic liquid” is an IL that is a liquid at temperatures below 100 degrees Celsius.
  • Phases which are "adjacent" to another phase may optionally be physically separated by an interface layer.
  • AIE Analyte Insensitive Electrode
  • typical voltammetric or amperometric electrochemical sensing systems typically comprised three electrodes, the working electrode, the reference electrode, and the counter electrode. Under conditions where little current flows through the sensing system, the reference and counter electrode functions can be combined into a single electrode resulting in a two-electrode system (working and reference/counter).
  • the sensing system functions by monitoring the current flow through the WE as a function of the applied potential. The applied potential is monitored by the RE, while the potential and current are supplied to the sample by the CE. The potential sensed by the RE is continuously compared with the desired waveform output by the controller/processor device. If the potential recorded by the RE does not reflect the desired potential, then the counter electrode is adjusted until the RE potential and the desired potential match.
  • the accuracy of the current versus voltage response of the system therefore depends on the ability of the RE to measure the potential at the WE accurately. High accuracy thus necessitates a highly stable RE that effectively measures the potential without being affected by the sample or duration of measurement.
  • the silver/silver chloride and saturated calomel electrodes are examples of such conventional reference electrodes (CREs).
  • CREs such as silver/silver chloride and saturated calomel electrodes have several disadvantages. There remains a need for a system that circumvents these disadvantages.
  • the present invention addresses this by loosening the stability requirement of the RE via introduction of a fourth electrode, the AIE. Due to this relaxation in stability, simple pseudo reference electrodes (PREs), such as the silver wire, may be used as REs. Functionally the AIE behaves as an additional WE with the exception that the AIE response, being independent of analyte, is always fixed relative to a known response such as the standard hydrogen electrode (SHE). Thus, instability in a given RE can be corrected by comparison with the known fixed response of the AIE.
  • PREs pseudo reference electrodes
  • SHE standard hydrogen electrode
  • the utility of the AIE of the invention arises, at least in part, from its ability to improve the stability and longevity of the AIM across both time and analyte composition. These improvements act to increase the performance and scope of applicability of the AIM compared to the prior art. Furthermore, the AIE construct relaxes the requirement that the RAM employed be insensitive to pH or other analytes of interest, thus broadening the range of RAMs that may be used to include not only AIMs but ASMs as well.
  • the present invention provides an electrode that renders redox materials contained therein insensitive to non-electrical external influences (e.g. analyte concentrations) while maintaining electrical contact with the balance of the components of the sensing system.
  • the electrode of the invention is therefore an analyte insensitive electrode (AIE). Due to this analyte insensitivity, the signal response of the AIE is independent of the environment in which the sensing system is placed, and therefore can be used as an internal calibration point.
  • the AIE can comprise a redox active material that is itself insensitive to the analyte (i.e. an analyte insensitive material or AIM) independent from the construct.
  • the AIE may comprise a redox material which is itself sensitive to the analyte (i.e. an analyte sensitive material or ASM) independent from the construct, but which is rendered insensitive to the analyte when used as the redox component of the AIE.
  • ASM an analyte sensitive material
  • AIE Analyte Insensitive Electrode
  • An AIE of the present invention can be viewed as a special class of WE in that it operates in much the same way as the WE described above, except that the measured AIE response is substantially insensitive to changes in the composition and/or presence of analyte(s) within the test solution. It does, however, comprise a redox-active species and so provides an electrochemical response, but one which is independent of any changes to the test solution composition (apart from a minimum threshold of supporting electrolyte) or the presence of any analyte. Thus, the AIE provides a constant, fixed electrochemical response, the nature of which depends on the mode of operation.
  • the AIE of the invention can produce a signal which has a constant peak current or alternatively a constant peak potential relative to the standard hydrogen electrode (SHE) or it may have both fixed peak current and fixed peak potential (relative to the SHE).
  • This signal can then be used as an internal standard from which the signal at the WE produced due to the presence of some target analyte(s) may be calibrated. Because this signal is constant relative to a known fixed quantity, such as the SHE, it may be used in practice with a less stable reference electrode such as a PRE thus providing a stable signal for internal calibration without the use of a conventional reference electrode.
  • the invention provides a multi-phase AIE for use in a voltammetric and/or amperometric electrochemical sensor system for measuring the presence and/or concentration of an analyte in a sample.
  • the AIE provides a predictable analyte-insensitive signal which is used as a standard of comparison for the signal generated using an ASM at the working electrode, and thereby allows an end user to determine an analyte's presence and/or concentration.
  • the AIE provided by the invention can include the following components: an electrolytic layer, a redox active material (RAM), a conductive component, and, optionally, a conductive physical barrier. In some embodiments, one or more of these components may be combined together. For instance, the RAM may be dispersed in the electrolytic layer and/or the electrolytic layer may saturate the pores of the conductive physical barrier. In other embodiments, the AIE optionally includes more than one of any one or more of the components described above.
  • the conductive physical barrier when present, serves to separate physically the other components of the AIE from the analyte. This physical separation attenuates the direct chemical interaction of the remainder of the AIE with the analyte, thereby minimizing effects such as convective mixing between the analyte and electrolytic layer. This in turn minimizes the change in composition of the electrolytic layer due to interaction with the analyte.
  • a requirement of the conductive physical barrier is that it effectively conducts the current necessary for generating the electrical signal associated with the redox active material.
  • Some embodiments of the invention have a single conductive physical barrier between the electrolytic layer and the analyte, while other embodiments include additional conductive physical barriers that serve to separate physically but maintain electrical contact between multiple electrolytic layers within the AIE.
  • a conductive physical barrier is present at the open end of the AIE housing, interposed between the sample and the contents of the AIE cavity, to contain the contents within the AIE cavity.
  • one or more internal conductive physical barriers are present within the AIE cavity, at the interface between any two of the component phases within the AIE cavity, to separate those two phases from each other physically.
  • the conductive physical barrier comprises a RAM.
  • the RAM may be dispersed in a conductive physical barrier.
  • a conductive physical barrier is a membrane containing an IL containing the RAM.
  • the conductive barrier is a polyethersulfone membrane.
  • the conductive physical barrier is a PVDF (polyvinylidene difluoride) membrane. Additional embodiments may combine the conductive physical barrier with the electrolytic layer into one component.
  • the electrolytic layer (e.g. composed of an RTIL or other suitable material, as described herein) provides the constant chemical environment and ionic strength for the RAM and provides a layer that limits or eliminates direct chemical interaction of the RAM with the sample being analyzed. Selection criteria for the electrolytic layer include (a) that its component composition must remain substantially unchanged over the lifetime of the AIE, (b) that it effectively conducts the current necessary for generating the electrical signal associated with the redox active material, and, optionally, (c) that it be substantially immiscible with the sample being analyzed.
  • the electrolytic layer is comprised of a fluorous layer with a dispersed electrolyte.
  • Suitable fluorous organic liquids include but are not limited to perfluoroaromatic compounds (e.g. hexafluorobenzene), perfluoroalkanes (e.g. tetradecafluorohexane, octadecafluorooctane, eicosafluorononane, and decafluoropentane) and alkyl perfluoroalkyl ethers (e.g. nonafluorobutyl methyl ether).
  • the dispersed electrolyte for the fluorous layer can be but is not limited to a fluorous ionic liquid (for examples see: Chem. Comm. 2000, 2051-2052 .
  • the electrolytic layer is a fluorous phase comprising a fluorous organic liquid and a dispersed electrolyte that is adjacent to but substantially immiscible with the sample.
  • the fluorous phase is at least 50% or at least 90% by weight of one or more fluorous organic compounds and the balance of the phase is comprised of one or more diluents including but not limited to gelling agents, electrolytes, organic solvents, water, inorganic compounds including salts, organic compounds, carbon allotropes, and redox active materials.
  • more than one fluorous phase may be present.
  • the electrolytic layer is comprised of an organic layer with a dispersed electrolyte.
  • a phase transfer agent dissolved in a common organic solvent e.g. tetrabutyl ammonium bromide in toluene
  • a suitable electrolytic layer e.g. tetrabutyl ammonium bromide in toluene
  • the electrolytic layer is an organic phase comprising an organic liquid adjacent to but substantially immiscible with the sample.
  • the composition of the organic phase is at least 50% or at least 90% by weight of one or more organic compounds and the balance of the phase is comprised of one or more diluents including but not limited to gelling agents, electrolytes, water, inorganic compounds including salts, organic compounds, carbon allotropes, and redox active materials.
  • more than one organic phase may be present.
  • the electrolytic layer is comprised of an aqueous layer with a dispersed electrolyte.
  • the aqueous layer is comprised substantially of water but may also include one or more diluents including but not limited to gelling agents, organic solvents, inorganic compounds including salts, organic compounds, carbon allotropes, and redox active materials.
  • the dispersed electrolyte comprises a salt of anions and cations chosen from a group including but not limited to inorganic, organic, and/or polymeric ions. In one embodiment the dispersed electrolyte is potassium chloride.
  • the electrolytic layer phase generally includes at least one IL that is substantially immiscible with the sample or with any intermediary electrolytic layers or phases, when such phases are present.
  • This quality of substantial immiscibility may be achieved as a result of the intrinsic properties of the IL itself, or may be the result of components such as a conductive physical barrier present in the construct (e.g. a porous frit) separating the phases or a membrane separating the phases.
  • the particular components of the IL phase may be chosen to achieve desired characteristics, which may include but are not limited to sample immiscibility; temperature stability; viscosity, dielectric constant; specific ionic chemical composition, and phase state at temperatures characteristic of particular applications.
  • the IL components are chosen so as to be liquid at a temperature or within a range of temperatures that include the temperature within which the sample will be measured. Suitable temperature ranges include but are not limited to between 10 degrees to 50 degrees Celsius; alternately from about 16 degrees to about 45 degrees Celsius; alternately from about 20 degrees to about 40 degrees Celsius.
  • the electrolytic layer is an ionic liquid (IL) composed of an anionic chemical species and a cationic chemical species and located adjacent to the sample but substantially immiscible with the sample.
  • IL ionic liquid
  • the composition of the IL phase is at least 50% or at least 90% by weight of one or more ionic liquids and the balance of the phase is comprised of one or more diluents including but not limited to gelling agents, electrolytes, organic solvents, water, inorganic compounds including salts, organic compounds, carbon allotropes, and redox active materials,
  • the composition of the IL phase is 100% of one or more ionic liquids.
  • Illustrative IL cations include but are not limited to quaternary pyrrolidines and N,N'-disubstituted imidazoles.
  • Illustrative IL anions include but are not limited to imides and borates, phosphates, and sulphates, which may be substituted as appropriate to form an anion of interest.
  • the IL cation is selected from a group that includes but is not limited to imidazolium (for example, 1-butyl-3-methylimidazolium, C 4 mim), pyridinium (for example, N-butyl pyridinium (C 4 py)), pyrrolidinium (for example, N-butyl-N-methyl pyrrolidinium (C 4 mpyrr)), tetraalkylammonium, and tetraalkylphosphonium.
  • imidazolium for example, 1-butyl-3-methylimidazolium, C 4 mim
  • pyridinium for example, N-butyl pyridinium (C 4 py)
  • pyrrolidinium for example, N-butyl-N-methyl pyrrolidinium (C 4 mpyrr)
  • tetraalkylammonium for example, N-butyl-N-methyl pyrrolidinium (C 4 mpyr
  • the IL anion is selected from a group that includes but is not limited to tetrafluoroborate (BF 4 ), bis(trifluoromethanesulfonyl)imide (N(Tf) 2 ), thiocyanate (SCN), dicyanamide (N(CN) 2 ), ethyl sulphate ((EtSO 4 ), hexafluorophosphate, (PF 6 ) and trifluorotris(pentafluoroethyl)phosphate (FAP).
  • the IL is an RTIL.
  • the RTIL phase is N-butyl-N-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C 4 mpyrr] [N(Tf) 2 ]).
  • the electrolytic layer comprises a microporous material wherein the IL or RTIL is immobilized within its interconnected micropores.
  • silica based sol-gels can be formed in the presence of ILs resulting in an ionogel which is conductive as a result of the IL contained therein (for example see: Chem. Mater., 2006, 18 (17), pp 3931-3936 ).
  • microporous materials suitable for use in the AlEs of the invention include those well known in the field of synthetic membranes. Membranes used for selective separations cover a broad range of pore sizes ranging from micrometers to nanometers, and may be derived from organic materials, especially polymers. For example, microporous membranes based on polysulfone, polyethersulfone, polyvinylidenefluoride, polytetrafluoroethylene, and certain derivatives based on those polymers generally exhibit good chemical stability toward both typical analyte solutions and the RTIL, and are thus suitable media for immobilizing the RTIL In this case the RTIL is the principal conduit of charge transfer across the electrolytic layer.
  • the electrolytic layer is a thin layer of nonporous solid material, for example a polymer film, in which the RTIL exhibits some solubility.
  • the polymer film containing dissolved RTIL can be considered as a solid solution, in that it exhibits the ionic conducting characteristic of the RTIL, but retains the dimensional stability of a solid.
  • a nonporous solid solution film can be made extremely thin without developing defects or pinholes.
  • nonporous polymer films include, but are not limited to, cross-linked derivatives of polyimidazole, poly(vinyl alcohol), poly(vinyl acetate), poly(ethylene oxide), and their copolymers or blends.
  • Conductivity in the solid solution film may be established at different loading, or concentration, of RTIL in different polymers.
  • Non-cross-linked polymers may be used where a relatively low loading of RTIL is sufficient to obtain conductivity.
  • Cross-linked polymers are preferred at relatively high loadings of RTIL to prevent excessive swelling or dissolution.
  • the solid solution of RTIL is a substantially uniform conduit of charges.
  • the solid solution film can be surface-modified to manipulate its selectivity toward hydrogen ions.
  • the AIE optionally includes an additional electrolytic layer.
  • an electrolytic layer is adjacent to the sample, and an additional electrolytic layer is interposed between any of the other phases of the electrode.
  • two electrolytic layers may be adjacent to each other.
  • Selection criteria for the additional electrolytic layer include the criteria described above for electrolytic layers.
  • Selection criteria for an additional electrolytic layer composition include but are not limited to viscosity and dielectric constant.
  • Exemplary materials include but are not limited to materials as described above for the first electrolytic layer, an ionic liquid, an aqueous electrolyte solution, a gelled aqueous electrolyte solution, an electrolyte containing sol-gel, an electrically conductive sol-gel, an organic solvent, and an organic electrolyte solution.
  • an electrolytic layer comprises one or more RAMs.
  • RAMs suitable for use in an electrolytic layer include, but are not limited to, the RAMs described below.
  • RAMs Redox active materials
  • Selection criteria for suitable RAMs that are a component of the AIE of the present invention include, but are not limited to, oxidation and/or reduction peaks obtained during voltammetric and/or amperometric measurements which are well-defined and are either substantially constant or vary in a definable manner.
  • an AIM or an ASM can be used in the AIE of the invention.
  • an ASM is effectively transformed into an AIM due to being isolated from the sample by the electrolytic layer.
  • AQ and PAQ are ASMs, but if they are isolated from any test solution either by being dispersed in the electrolytic layer or in contact with an aqueous phase of fixed pH behind the electrolytic layer, and the electrolytic layer (e.g the RTIL) prevents the transfer of protons, then there is one fixed signal (the non-aqueous voltammetry of AQ or PAQ in the electrolytic layer) or the usual (but constant) signal in the aqueous layer.
  • the ASM would then be considered an AIM within the context of this embodiment of the invention.
  • the AIE construct thus confers analyte insensitivity to an ASM.
  • Suitable redox active materials for use in the AIE of the present invention are reversible, quasi-reversible and irreversible redox-active compounds, including but not limited to redox-active organic molecules, redox-active polymers, metal complexes, organometallic species, metals, metal salts or semiconductors, present as liquids or solids formed as bulk materials, microparticles or nanoparticles, that undergo one or more electron transfer processes not involving reaction with the target analyte and whose redox behaviors are therefore insensitive to the presence of the target analyte.
  • an ASM can also be used to form the AIE of the invention if it is isolated from the sample by the electrolytic layer.
  • the RAM is selected from compounds that include but are not limited to, ferrocene or ferrocene derivatives including but not limited to ferrocene derivatives comprising alkyl, aryl and heteroatomic substituents on one or both cyclopentadienyl rings; polymers of variable cross-linking comprising ferrocene and other non-redox-active monomers such as styrene and acrylates, silver nanoparticles on carbon substrates such as glassy carbon, graphite, and carbon nanotubes (CNTs), hexacyano iron compounds with variable counter-ions including but not limited to main group and transition metal cations, and other redox-active transition metal complexes.
  • ferrocene or ferrocene derivatives including but not limited to ferrocene derivatives comprising alkyl, aryl and heteroatomic substituents on one or both cyclopentadienyl rings
  • polymers of variable cross-linking comprising ferrocene and other non-re
  • the RAM is n-butyl-ferrocene, silver nanoparticle modified glassy carbon powder (AG-np-GC), ferrocene, polyvinylferrocene, nickelhexacyanoferrate, ferrocene styrene copolymers, ferrocene styrene cross-linked copolymers, Ni Cyclam, or K 4 Fe(CN) 6 .
  • the AIM is n-butyl-ferrocene.
  • the AIM is K 4 Fe(CN) 6 . This list is not exhaustive and is not intended to be limiting. One skilled in the art will be able to identify and use many other RAMs in place of or in addition to those listed above.
  • an ASM can serve the same function as an AIM in the AIE construct.
  • Suitable ASMs for use in the AIE include but are not limited to anthraquinone (AQ), anthracene, 9,10-phenanthrenequinone (PAQ), 1,4-benzoquinone, 1,2-benzoquinone, 1,4-napthaquinone, 1,2-napthaquinone, N,N'-diphenyl-p-phenylenediamine (DPPD), azo containing compounds such as azobenzene and derivatives thereof, porphyrins and derivatives thereof such as octaethylporphyrin or tetraphenylporphyrins, metalloporphyrins and derivatives thereof such as hemin, iron octaethylprophyrin, iron tetraphenylporphyrin, and viologens and derivatives thereof such as methyl viologen.
  • This list is not exhaustive and is
  • One or more RAMs may be dispersed in one or more of any of the electrolytic layers (e.g the IL) or the external conductive physical barrier or the conductive component, or may be dispersed in an internal conductive physical barrier. In other embodiments, a single RAM is dispersed in one or more of the electrolytic layers (e.g. the IL) or in the conductive component. In another embodiment, different RAMs are dispersed in one or more electrolytic layers or in the conductive component.
  • the AIE of the current invention includes a conductive component.
  • the conductive component is a conductive backing located at the rear of the AIE cavity and forming the rear wall of the cavity.
  • a conductive lead (sometimes referred to herein as a transmission element) is electrically connected to the backing (i.e. by being soldered to the backing), and protrudes through the rear bore, which may optionally be sealed with one or more materials including but not limited to a silicone polymer, including a substituted silicone polymer and an epoxy composition.
  • the lead provides a means of transmitting electrical signals to and from the electrode.
  • conductive materials may be used for the conductive backing, including but not limited to carbon allotropes and derivatives thereof, transition metals (e.g platinum, gold, and mercury), conductive metal alloys, conductive polymeric compounds and derivatives thereof, semiconductor materials and derivatives thereof, including silicon and derivatives thereof, and additional suitable materials not specifically mentioned.
  • transition metals e.g platinum, gold, and mercury
  • conductive metal alloys e.g platinum, gold, and mercury
  • conductive polymeric compounds and derivatives thereof e.g., polymeric compounds and derivatives thereof
  • semiconductor materials and derivatives thereof including silicon and derivatives thereof, and additional suitable materials not specifically mentioned.
  • a RAM is associated with the conductive backing by methods including but not limited to abrasive immobilization, adsorption, electrostatic binding or covalent binding to the backing surface.
  • Suitable RAMs for associating with the conductive backing include but are not limited to those specified in the preceding section.
  • the conductive component may comprise a plug of conductive material in addition to or in place of the conductive backing.
  • the transmission element is electrically connected to the plug.
  • the plug contains a binder and at least one electrically conductive material.
  • Suitable binders include but are not limited to epoxy, mineral oil and polymer binders.
  • Suitable conductive materials include but are not limited to graphite, MWCNTs, SWCNTs, glassy carbon, as well as those discussed above as materials useful for the conductive backing.
  • the plug is a mixture of epoxy and graphite. In another embodiment, the plug is a mixture of epoxy, graphite and MWCNTs. In another embodiment, the plug is a mixture of epoxy, graphite and SWCNTs. In another embodiment, the plug is a mixture of epoxy, graphite and glassy carbon. In another embodiment, the plug is formed using epoxy and MWCNTs. In another embodiment, the plug is formed using epoxy and SWCNTs. In another embodiment, the plug is formed using epoxy and glassy carbon.
  • one or more RAMs are present in the composite plug, in addition to the binder and the conductive material. RAMs suitable for associating with or incorporating into the conductive plug include but are not limited to those specified in the preceding section.
  • the RAM is mixed with the binder and the conductive material.
  • the RAM is associated with one of the components of the composite material, by methods including but not limited to abrasive immobilization, adsorption, electrostatic binding or covalent binding.
  • the components are combined via mechanical mixing using a mortar and pestle.
  • the components are mixed in an organic solvent.
  • aspects of the AIE include a cylindrical housing (1) with the conductive backing (5) of the conductive component (4) defining an AIE cavity (3) having a sample end (12).
  • a conductive lead (2) is attached and in electrical connection with the conductive plate and protrudes through the rear bore, providing a means for transmitting electrical signals to and from the AIE.
  • the conductive component optionally includes a plug of conductive composite material (6) in the AIE cavity in electrical contact with and adjacent to the conductive backing.
  • a first electrolytic layer (e.g IL phase) (7) is adjacent to the conductive component, and contained within the AIE cavity by a first, external, conductive physical barrier (8).
  • additional electrolytic layers e.g. IL phases
  • an additional electrolytic layer (10) is located between the conductive component and the first electrolytic layer (e.g. IL phase), and is separated from the first electrolytic layer (e.g. IL phase) by a conductive physical barrier (9).
  • additional electrolytic layers may be present.
  • the RAM may be dispersed in the conductive component, optionally in either the conductive backing and/or the composite plug, or in any of the electrolytic layers (e.g. IL layers).
  • the analyte is chemically isolated from the RAM by the electrolytic layer (e.g. IL layer).
  • the RAM may be further chemically isolated or physically isolated from the analyte by an additional electrolytic layer.
  • the conductive component (4) includes a conductive composite plug (6) and an electrolytic layer (e.g. an IL phase) (7), contained by an external conductive physical barrier (8).
  • an electrolytic layer e.g. an IL phase
  • the same or different RAMs are dispersed within both the plug and the electrolytic layer (e.g. IL phase).
  • a second electrolytic layer (10) is added between the conductive material plug and the first electrolytic layer (e.g. IL phase).
  • the second electrolytic layer may be in direct contact with the first electrolytic layer (e.g. IL phase); alternatively, a first internal conductive physical barrier (9) may separate the second electrolytic layer from the first electrolytic layer (e.g. IL phase).
  • One or more RAMs may be dispersed in the conductive component or the electrolytic layers (e.g. IL phase).
  • the present invention provides a multi-phase AIE for use in an electrochemical sensing device for measuring an analyte in a sample, the AIE comprising (a) an electrolytic layer; (b) an electrically conductive component electrically connected to the electrolytic layer, and (c) a redox active material (RAM), capable of being electrically oxidized and/or electrically reduced, wherein the redox activity of the material is substantially insensitive to the analyte, and wherein further the RAM may be dispersed in either the electrolytic layer or the conductive component.
  • AIE comprising (a) an electrolytic layer; (b) an electrically conductive component electrically connected to the electrolytic layer, and (c) a redox active material (RAM), capable of being electrically oxidized and/or electrically reduced, wherein the redox activity of the material is substantially insensitive to the analyte, and wherein further the RAM may be dispersed in either the electrolytic layer or the conductive component.
  • RAM redox active material
  • the present invention provides an electrochemical sensor system for measuring the presence and/or concentration of an analyte in a sample.
  • Various embodiments of the invention are possible, which have in common an embodiment of the AIE of the present invention, a working electrode, optionally a counter electrode, a reference or pseudo-reference electrode and a controller device for supplying a range of electrical signals to the indicator and working electrodes, and measuring the electrical response of the working electrode and the AIE over the range of applied signals.
  • the analyte sensor system of the present invention includes an AIE as described above.
  • the analyte sensing system of the present invention further includes a working electrode.
  • Working electrodes suitable for use in the sensor system of the present invention are known in the art. See U.S. Pat. No. 5,223,117 , PCT Patent Publication Nos. 2005/066618 and 2007/034131 and GB Patent Publication No. 2409902 .
  • Working electrodes suitable for use in the sensing devices of the invention include, for example and without limitation, those described in provisional U.S. patent application Serial Nos. 61/161,139 , filed 25 Mar 09; 61/225,855 , filed 15 Jul 09; and 61/289,318 , filed 22 Dec 09.
  • Characteristic of the working electrode component of the present invention is that it allows the passage of current, in response to electrical perturbations of the sample, and demonstrates an electrochemical response that is sensitive to one or more analyte(s) in the system.
  • the WE may be chemically modified with analyte sensitive species or materials.
  • the WE is modified with at least one analyte-sensitive redox active material having well-defined oxidation and/or reduction peaks.
  • the general mode of operation of working electrodes in an electrochemical sensor system is known in the art.
  • an electrical signal (optionally, an applied potential relative to some thermodynamically fixed reference electrode potential)
  • the electrical response of the working electrode is measured and compared to a reference point provided by, for example, an external calibration plot in cases where the WE passes minimal current (potentiometric device), or, in embodiments of the present invention, to a reference point provided by the AIE.
  • the WE response is measured as a function of the potential difference applied between the WE and some suitable CRE/PRE.
  • the sensor system of the present invention includes a conventional reference electrode or, a pseudo-reference electrode.
  • a conventional reference electrode or, a pseudo-reference electrode examples of conventional reference electrodes and pseudo-reference electrodes are known in the art. See Bard and Faulkner, "Electrochemical Methods: Fundamentals and Applications” (Wiley 2001 ).
  • the CRE allows the application of a known, controlled potential difference to the WE by providing a fixed reference point.
  • a "pseudo-reference electrode” may be used. These typically do not comprise both halves of a well-defined redox potential, and are therefore not thermodynamic reference electrodes of fixed composition and potential. However, they are functionally simpler than a conventional RE and provide a reasonably constant potential over the timescale of an electrochemical experiment.
  • Use of the PRE in conjunction with an AIE of the present invention obviates the need for the conventional reference electrode thereby overcoming the disadvantages of the CRE.
  • One (but not exhaustive) example of a PRE is the use of a silver wire.
  • Counter electrodes suitable for use in the sensor system of the present invention are known in the art. See, for example, Bard and Faulkner, "Electrochemical Methods: Fundamentals and Applications” (Wiley 2001 ).
  • the CE is typically made of a relatively chemically inert material, commonly Pt or carbon (graphite).
  • Pt or carbon graphite
  • the CE serves as an electron source or sink, thereby delivering current to the sample and allowing it to flow through the sensor system.
  • the analyte sensor system of the present invention further includes a controller/processor device.
  • Controller/processor devices suitable for use in the analyte sensor system of the invention include, for example and without limitation, those described in provisional U.S. patent application Serial Nos. 61/161,139, filed 25 Mar 2009 ; 61/225,855, filed 15 Jul 2009 ; 61/289,318, filed 22 Dec 2009 ; 61/308,244, filed 25 Feb 2010 ; and 61/309,182, filed 1 Mar 2010 .
  • the controller/processor device is a single-channel device through which the working electrode and AIE are electrically connected and controlled, and their signals recorded, on the same channel.
  • single channel controllers examples include a potentiostat and a galvanostat.
  • the working electrode and the AIE are physically remote and connected by a multi-channel device capable of controlling and/or recording signals from the working electrode and the AIE independently.
  • the controller/processor device is a multichannel potentiostat.
  • the signals from the working electrode and AIE are combined and the processor then analyzes the data from the combined signal.
  • the signals from the working electrode and AIE are recorded separately and subsequently combined and analyzed by the processor.
  • the electrical responses of the AIE as incorporated in embodiments of the sensor system of the present invention are determined using methods including but not limited to cyclic or square-wave voltammetry as described in the "Materials and Methods" section of the Example below.
  • embodiments of the present invention upon being subjected to cyclic or square wave voltammetry, embodiments of the present invention give an electrical response that is substantially constant or varies in a substantially predictable manner.
  • the invention has application in all areas involving voltammetric and amperometric sensing, including but not limited to the detection of metal ions, metal complexes and derivatives (e.g. As(III), Pb(II), Fe(II/III), Cu(II/I), Hg(II), and many others), the detection of pollutants (e.g. chlorinated phenols/organics, pesticides, herbicides, nitrite/nitrate, and the like), gas sensing both directly in air and dissolved gases in aqueous media (e.g.
  • pollutants e.g. chlorinated phenols/organics, pesticides, herbicides, nitrite/nitrate, and the like
  • gas sensing both directly in air and dissolved gases in aqueous media e.g.
  • CO 2 , CO, SO 2 and H 2 S in particular - important in the petrochemical and automobile industries, among many others), environmental monitoring (WHO, US EPA, and EU regulatory bodies), drug detection (e.g. the OxTox drug testing unit), food industry Q&A (e.g. capsaicin in spicy foods, hesperidin in citrus fruit juices, and the like), medical and (bio)pharmaceutical Q&A, diagnostics/accreditation, and glucose sensing (diabetes, home monitoring). Accordingly, those of skill in the art will recognize that the devices and methods of the present invention are illustrated by but are not limited by the examples that follow.
  • a graphite/epoxy composite was prepared by combining 300 mg graphite with 1.15 grams of epoxy A and 150 mg of epoxy B (Epoxy Technology, Bellerica, MD) using a mortar and pestle.
  • Multi-walled Carbon Nanotube MWCNT
  • Graphite Graphite / Epoxy Composite with n-butyl-ferrocene
  • a MWCNT/graphite/epoxy composite containing n-butyl-ferrocene was prepared by combining, in dichloromethane, 17mg of multi-walled bamboo-type MWCNTs (bamboo type 5 to 20 ⁇ m in length and having an outer wall diameter of 30 +/- 15 nm) (Nanolab, Brighton, MA) with 17mg of graphite, 20 mg of n-butyl-ferrocene, 200 mg of epoxy A and 30 mg of epoxy B. The solvent was then evaporated at room temperature.
  • a conductive plug optionally with a RAM dispersed in it, was first formed within the AIE cavity, on top of the brass plate opposite the brass lead, and flush with the sample end of the housing, by packing the AIE cavity with one of the uncured conductive composite materials described above. After curing (by baking at 150 degrees C for 1 hour), the exposed end of the plug was cleaned and polished. A polymeric collar having an internal diameter identical to the external diameter of the housing was then fitted over the sample end of the housing, thereby elongating the AIE cavity in which the AIE phase layers were placed.
  • a first PEEK washer having an internal diameter of 4,763 mm (3/16 inch) and an outer diameter identical to the internal diameter of the AIE cavity was then placed in the AIE cavity and tamped until flush with the plug, forming a well.
  • a drop of RTIL phase was then deposited in the well, followed by a polyethersulfone membrane (i.e. the conductive physical barrier) having the same diameter as the washer, and a second PEEK washer placed on top of the membrane.
  • the plug is recessed, and the PEEK washer adjacent to the plug is omitted.
  • the RTIL phase is layered directly on the plug surface.
  • a polyethersulfone membrane is then placed over the end of the AIE cavity.
  • an additional electrolytic layer which may optionally comprise an RAM dispersed in it is interposed between the RTIL (i.e. the first electrolytic layer) phase and the sample, by placing one drop of the second electrolytic layer solution in the well formed by the washer adjacent to the composite plug, followed by a polyethersulfone membrane and another PEEK washer.
  • a second RTIL phase layer (i.e a second electrolytic layer) which may optionally comprise a RAM dispersed in it is interposed between the first electrolytic layer and the composite plug by placing one drop of the second RTIL phase in the well formed by the washer adjacent to the composite plug, followed by a polyethersulfone membrane and a PEEK washer.
  • the layers were compressed by placing the probe lengthwise in a C-clamp and exerting sufficient pressure to bring the end of the electrode collar and the contents of the housing flush with the edge of the housing's sample.
  • Square wave or cyclic voltammetric measurements were made using a standard three-electrode configuration using an ECHOCHEMIE AUTOLAB potentiostat/galvanometer (model PGSTAT12) with the AIE acting as the working electrode, a saturated calomel electrode functioning as a reference, and a graphite rod serving as a counter-electrode.
  • the sample end of the AIE, the sensor end of the calomel reference, and the counter-electrode were placed in contact with a buffer solution of defined pH. The system was then subject to oxidative or reductive cycles of square-wave voltammetry over a range of potentials and the resulting current through the AIE was measured as a function of the applied potential.
  • a first exemplary AIE having a second electrolytic layer with the RAM in the RTIL phase (i.e. the first electrolytic phase) was constructed as described in the materials and methods section above using a graphite/epoxy plug, 1 drop of 1M KCl for the second electrolytic phase and 1 drop of a 1% volume:volume solution of n-butyl-ferrocene in [C 4 mpyrr][N(Tf) 2 ] for the RTIL phase.
  • a second exemplary AIE having an aqueous electrolytic phase and with the RAM in the RTIL phase was constructed in the same manner as the first, with the exception that one drop of 1M KCl in 2% HMW hydroxyethylcellulose gel was used for the second electrolytic phase.
  • a third exemplary embodiment having an aqueous electrolytic phase and with the RAM in the RTIL phase was constructed generally as described in the Materials and Methods section above, using a MWCNT/graphite/epoxy/n-butyl-ferrocene plug prepared with 17 mg MWCNT, 17 mg graphite, 200 mg epoxy A, 30 mg epoxy B and 20 mg of n-butyl-ferrocene.
  • the reagents were combined by stirring in methylene chloride and then evaporating the solvent at room temperature.
  • FIG. 5C is a plot showing the results from this control experiment in a plot overlayed with the data from the first 2000 scans of the experiment described in the preceding paragraph.
  • a fourth exemplary AIE having an aqueous electrolytic layer with one RAM in the aqueous electrolytic layer and another, different RAM in the RTIL phase was constructed using the same housing and graphite/epoxy plug as were used in the first embodiment. 1 drop of a solution of 1M KCl and 10 mM K 4 Fe(CN) 6 was used for the second electrolytic layer, and 1 drop of 1% volume:volume n-butyl-ferrocene in [C 4 mpyrr][N(Tf) 2 ] was used for the RTIL phase.
  • a fifth exemplary embodiment without a second electrolytic phase but containing a RAM in the composite plug was constructed generally as described in the materials and methods section above using a MWCNT/graphite/epoxy/ n-butyl-ferrocene plug prepared by combining 30mg of n-butyl-ferrocene, 49mg MWCNT, 49mg graphite, 575mg epoxy A and 56mg epoxy B in methylene chloride, stirring, then evaporating the solvent at room temperature.
  • the plug was recessed slightly in the housing. No washer was used adjacent to the plug; instead, 1 drop of [C 4 mpyrr][N(Tf) 2 ] deposited directly on the recessed plug was used as the RTIL electrolytic layer phase.
  • a polyethersulfone membrane was then used as the conductive physical barrier and layered directly over the RTIL phase, followed by a PEEK washer. This is depicted as configuration 1 in Figure 2 .
  • Square wave voltammetric measurements were then made from the fifth exemplary embodiment as described in the test protocol section above, for a total of 20 continuous oxidative cycles of square wave voltammetry over a potential range of -0.8 to +0.8V and the resulting current through the AIE as a function of the applied potential was measured.
  • the measurements were made at pH 2, 4, 7, 8, 9.18 and 10 using buffers having compositions shown in Table 1 and solutions of 10 mM HCl and 1000 mM KCl. The results are shown in Figures 6A and 6B .
  • a sixth exemplary embodiment without a second electrolytic layer and having the RAM in the plug was constructed with a MWCNT/graphite/epoxy/ plug.
  • the PEEK washer adjacent to the plug was omitted; instead, a polyethersulfone membrane wetted with 1% volume:volume solution of n-butyl-ferrocene in [C 4 mpyrr][N(Tf) 2 ] was placed on top of the plug, followed by a PEEK washer, and the electrode was then compressed as described above.
  • This embodiment is depicted in Figure 7 .

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Claims (13)

  1. Multiphasen-AIE (analytenunempfindliche Elektrode) zur Verwendung in einer elektrochemischen Sensorvorrichtung zum Messen eines Analyten in einer Probe, wobei die AIE umfasst:
    (a) eine Elektrolytschicht (7);
    (b) eine elektrisch leitfähige Komponente (4), die mit der Elektrolytschicht elektrisch verbunden ist;
    (c) ein redoxaktives Material, das elektrisch oxidiert und/oder elektrisch reduziert werden kann, wobei das redoxaktive Material in der Elektrolytschicht und/oder der leitfähigen Komponente dispergiert ist; und
    (d) eine leitfähige physikalische Sperre (8), die, wenn die Elektrode mit einer Probe in Kontakt ist, so positioniert ist, dass sie sich zwischen der Elektrolytschicht (7) und einer Probe befindet und die Elektrolytschicht (7) physikalisch von der Probe trennt.
  2. AIE gemäß Anspruch 1, wobei die Elektrolytschicht aus der Gruppe ausgewählt ist, die aus (i) einer ionischen Flüssigkeit (IL), die eine anionische chemische Spezies und eine kationische chemische Spezies umfasst, (ii) einer fluorhaltigen Phase, die eine fluorhaltige organische Flüssigkeit und einen dispergierten Elektrolyten umfasst, (iii) einer organischen Phase, die eine organische Flüssigkeit und einen dispergierten Elektrolyten umfasst, und (iv) einer wässrigen Phase, die Wasser und einen dispergierten Elektrolyten umfasst, besteht.
  3. AIE gemäß Anspruch 2, wobei die Elektrolytschicht eine ionische Flüssigkeit (IL) ist oder wobei die IL eine bei Raumtemperatur ionische Flüssigkeit (RTIL) ist.
  4. AIE gemäß Anspruch 1, wobei das redoxaktive Material aus der Gruppe ausgewählt ist, die aus einem redoxaktiven organischen Molekül, redoxaktiven Polymeren, Metallkomplexen, metallorganischen Spezies, Metallen, Metallsalzen oder Halbleitern besteht, und wobei das redoxaktive Material einen oder mehrere Elektronenübertragungsvorgänge erfährt oder wobei das redoxaktive Material aus der Gruppe ausgewählt ist, die aus n-Butylferrocen, mit Silbernanopartikeln beschichtetem Glaskohlenstoff, Ferrocen, Polyvinylferrocen, NiHCF, Ferrocen-Styrol-Copolymeren, vernetzten Ferrocen-Styrol-Copolymeren, Ni-Cyclam und K4Fe(CN)6, Anthrachinon (AQ), Anthracen, 9,10-Phenanthrenchinon (PAQ), 1,4-Benzochinon, 1,2-Benzochinon, 1,4-Napthochinon, 1,2-Napthochinon, N,N'-Diphenyl-p-phenylendiamin (DPPD), azohaltigen Verbindungen, Azobenzol und Derivaten davon, Porphyrinen und Derivaten davon, Octaethylporphyrin, Tetraphenylporphyrinen, Metalloporphyrinen und Derivaten davon,, Hämin, Eisenoctaethylporphyrin, Eisentetraphenylporphyrin und Viologenen und Derivaten davon und Methylviologen besteht.
  5. AIE gemäß Anspruch 1, wobei die leitfähige Komponente ein elektrisch leitfähiges Material umfasst, das aus der Gruppe ausgewählt ist, die aus Kohlenstoff-Allotropen und Derivaten davon, Übergangsmetallen und Derivaten davon, Postübergangsmetallen und Derivaten davon, leitfähigen Metalllegierungen und Derivaten davon, Silicium und Derivaten davon, leitfähigen polymeren Verbindungen und Derivaten davon sowie Halbleitermaterialien und Derivaten davon besteht.
  6. AIE gemäß Anspruch 1, wobei die leitfähige Komponente weiterhin einen Verbundstoff umfasst, der ein Bindemittel und ein elektrisch leitfähiges Material umfasst, wobei vorzugsweise das elektrisch leitfähige Material wenigstens eines aus Graphit, Glaskohlenstoff, mehrwandigen Kohlenstoffnanoröhrchen (MWCNTs), einwandigen Nanoröhrchen (SWNTs), bordotiertem Diamant und einer Kombination davon umfasst, wobei vorzugsweise der Verbundstoff weiterhin das redoxaktive Material umfasst, wobei es sich vorzugsweise bei dem redoxaktiven Material um n-Butylferrocen handelt.
  7. AIE gemäß Anspruch 5, wobei die leitfähige Komponente aus der Gruppe von Metallen ausgewählt ist, die Platin, Gold und Quecksilber umfasst.
  8. AIE gemäß Anspruch 1, wobei die leitfähige physikalische Sperre selektiv undurchlässig für einen Analyten oder für Nichtanalytenspezies in der Probe oder beides ist oder wobei die leitfähige physikalische Sperre aus der Gruppe ausgewählt ist, die aus einer porösen Fritte, einer Folie, einer mikroporösen Membran und einer nichtporösen Membran, die eine feste Lösung von IL in einem polymeren oder anorganischen Material umfasst, besteht, oder wobei es sich bei der Elektrolytschicht um die bei Raumtemperatur ionische Flüssigkeit (RTIL) N-Butyl-N-methylpyrrolidinium-bis(trifluormethansulfonyl)imid ([C4mpyrr][N(Tf)2]) handelt, die elektrisch leitfähige Komponente aus mehrwandigen Kohlenstoffnanoröhrchen, Graphit und Epoxid besteht, es sich bei dem redoxaktiven Material (RAM) um n-Butylferrocen handelt und die leitfähige Sperrschicht eine Polyethersulfonmembran in direktem Kontakt mit der RTIL und dadurch mit dieser gesättigt ist, oder weiterhin umfassend:
    (e) eine zweite Elektrolytphase, die an die erste Elektrolytschicht angrenzt und mit der ersten Elektrolytschicht im Wesentlichen unmischbar ist, wobei sich die zweite Elektrolytphase zwischen der leitfähigen Komponente und der ersten Elektrolytschicht befindet und in elektrischer Verbindung mit der ersten Elektrolytschicht und der leitfähigen Komponente steht, oder weiterhin umfassend:
    (f) eine zweite Elektrolytphase, wobei sich eine leitfähige physikalische Sperre zwischen der zweiten und der ersten Elektrolytschicht befindet, wobei das redoxaktive Material gegebenenfalls in der zweiten Elektrolytschicht dispergiert ist und wobei sich die zweite Elektrolytphase zwischen der leitfähigen Komponente und der ersten Elektrolytschicht befindet und in elektrischer Verbindung mit der ersten Elektrolytschicht und der leitfähigen Komponente steht.
  9. AIE gemäß Anspruch 8, wobei die zweite Elektrolytschicht in (e) aus der Gruppe ausgewählt ist, die aus einer wässrigen Elektrolytlösung, einer gelierten wässrigen Elektrolytlösung, einem elektrolytischen Sol-Gel, einer ionischen Flüssigkeit, einer elektrolythaltigen fluorhaltigen Schicht und einer organischen Elektrolytlösung besteht.
  10. Elektrochemische Sensorvorrichtung zum Messen eines Analyten in einer Probe, umfassend:
    (a) eine AIE gemäß Anspruch 1;
    (b) eine Arbeitselektrode in elektrischer Verbindung mit der AIE, wobei die Arbeitselektrode gegenüber dem Elektrolyten im Wesentlichen empfindlich ist; und
    (c) eine elektronische Steuervorrichtung in elektrischer Verbindung mit der AIE und der Arbeitselektrode, um ein elektrisches Signal an die AIE und die Arbeitselektrode zu senden und die elektrischen Antworten der AIE und der Arbeitselektrode zu empfangen.
  11. Vorrichtung gemäß Anspruch 10, wobei die AIE und die Arbeitselektrode innerhalb der elektronischen Steuervorrichtung parallel geschaltet sind oder wobei die AIE und die Arbeitselektrode konfigurationsmäßig vereinigt und durch eine gemeinsame leitfähige Komponente elektrisch miteinander verbunden sind oder wobei die elektronische Steuervorrichtung eine Einkanal-Steuervorrichtung ist und wobei weiterhin die AIE und die Arbeitselektrode durch die elektronische Einkanal-Steuervorrichtung elektrisch miteinander verbunden sind oder wobei die elektronische Steuervorrichtung eine Mehrkanal-Steuervorrichtung ist und wobei weiterhin die AIE und die Arbeitselektrode auf getrennten Datenkanälen innerhalb der elektronischen Mehrkanal-Steuervorrichtung miteinander verbunden sind, oder weiterhin umfassend eine herkömmliche Referenzelektrode mit einem festen elektrochemischen Potential, wobei die herkömmliche Referenzelektrode elektrisch mit der AIE, der Arbeitselektrode und der elektronischen Steuer-/Prozessor-Vorrichtung verbunden ist, oder weiterhin umfassend eine Gegenelektrode, wobei die Gegenelektrode elektrisch mit der AIE, der Arbeitselektrode, der herkömmlichen Referenzelektrode und der elektronischen Steuer-/Prozessor-Vorrichtung verbunden ist.
  12. Verfahren zum Messen eines Analyten in einer Probe unter Verwendung der Sensorvorrichtung gemäß Anspruch 10, umfassend die Schritte:
    (a) In-Kontakt-Bringen der Vorrichtung mit der Probe;
    (b) Senden eines elektrischen Signals an die AIE; und
    (c) Messen der elektrischen Antwort der AIE;
    wobei die elektrische Antwort der AIE von der Analytenkonzentration in der Probe unabhängig ist.
  13. Verfahren gemäß Anspruch 12, wobei nach dem Senden des elektrischen Signals an die AIE die gemessene elektrische Antwort der AIE unabhängig von dem Analyten relativ zu einem Referenzpotential im Wesentlichen konstant bleibt oder wobei nach dem Senden des elektrischen Signals an die AIE die gemessene elektrische Antwort der AIE unabhängig von dem Analyten in einer im Wesentlichen vorhersagbaren Weise relativ zu einem Referenzpotential variiert.
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Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8197650B2 (en) 2007-06-07 2012-06-12 Sensor Innovations, Inc. Silicon electrochemical sensors
TWI502195B (zh) * 2009-03-10 2015-10-01 Senova Systems Inc 在用於測量樣品中之分析物的電化學感測裝置中所用的多相分析物非敏感性電極、包含此電極的電化學感測裝置，與使用此感測裝置測量樣品中之分析物的方法
EP2411793B1 (de) 2009-03-25 2019-05-08 Parker-Hannifin Corporation pH MESSVORRICHTUNG
JP5937592B2 (ja) 2010-07-26 2016-06-22 セノバ システムズ インコーポレイテッド 分析物センサー
WO2012083258A2 (en) 2010-12-16 2012-06-21 Sensor Innovations, Inc. Electrochemical sensors
WO2013039858A2 (en) * 2011-09-12 2013-03-21 Nanoselect, Inc. Carbon nanostructure electrochemical sensor and method
GB2497972B (en) * 2011-12-23 2016-03-16 Schlumberger Holdings Electrochemical sensors
BR112014015708A8 (pt) * 2011-12-23 2017-07-04 Prad Res & Development Ltd método para determinar o ph de um líquido aquoso, aparelho para determinar ph de um líquido aquoso, e equipamento para processar um líquido aquoso
WO2013112767A1 (en) * 2012-01-25 2013-08-01 Senova Systems, Inc. Analyte sensor
US9632053B2 (en) 2012-03-08 2017-04-25 Parker-Hannifin Corporation Analyte sensing device
CN105122047A (zh) 2012-12-27 2015-12-02 赛诺瓦系统股份有限公司 pH计
DE102013003559B4 (de) * 2013-03-01 2014-12-11 Compur Monitors Gmbh & Co. Kg Verfahren zur Erzeugung von Blausäuregas in einer elektrochemischen Zelle
US10538635B2 (en) * 2014-06-11 2020-01-21 Parker-Hannifin Corporation Solid state electrodes and sensors
MX2018000838A (es) 2015-07-29 2018-08-15 Parker Hannifin Corp Electrodos en estado solido y sensores que tienen areas de superficie activas redox.
WO2017223365A1 (en) * 2016-06-23 2017-12-28 Hach Company Alkalinity sensor
US11307168B2 (en) 2017-02-13 2022-04-19 Anb Sensors Limited Online reference calibration
TWI631932B (zh) 2017-03-15 2018-08-11 奇翼醫電股份有限公司 生理訊號接收裝置及其製造方法
JP7438099B2 (ja) * 2017-04-03 2024-02-26 ラジオメーター・メディカル・アー・ペー・エス 基準流体を収容している袋
CN110678746A (zh) * 2017-05-03 2020-01-10 戴卫凯尔有限公司 一次性电化学传感条带及相关方法
CN109142474B (zh) * 2017-06-27 2020-07-14 华东师范大学 一种可同时检测Cu+和pH的碳纳米材料修饰电极及制备方法
EP3695216A4 (de) * 2017-10-11 2021-08-18 ANB Sensors Limited Kalibrierelektrode
GB201720353D0 (en) * 2017-12-06 2018-01-17 Anb Sensors Ltd Smart medical/pharmaceutical sensor
DE102018128895A1 (de) 2017-12-19 2019-06-19 Endress+Hauser Conducta Gmbh+Co. Kg Bezugselektrode und Verfahren zur Herstellung einer Bezugselektrode
CN108362749B (zh) * 2018-01-23 2020-02-14 常州大学 一种可用于检测没食子酸的凹凸棒石-离子液体/聚间苯二胺修饰电极的制备方法
EP3588634B1 (de) * 2018-06-27 2023-11-22 InnovationLab GmbH Verbessertes organisches elektrodenmaterial
US11035822B2 (en) 2018-09-06 2021-06-15 Robert Bosch Gmbh PH sensing method based upon the potential difference between two electrochemical waves
CN110133089B (zh) * 2019-05-31 2021-12-21 广州钰芯传感科技有限公司 一种电化学传感器自动内校准系统及校准方法
AU2020294096A1 (en) * 2019-06-12 2022-01-06 The Regents Of The University Of California Modulating electron transfer kinetics in E-DNA-type sensors
EP4095524A4 (de) * 2020-03-03 2024-03-06 HORIBA Advanced Techno, Co., Ltd. Ionische flüssigkeit enthaltendes polymer
US20210364506A1 (en) * 2020-05-22 2021-11-25 Robert Bosch Gmbh Methods for detecting an amount of an analyte in a solution
CN112268947B (zh) * 2020-10-23 2024-09-06 江苏英诺麦德科技有限公司 一种微型电化学传感器自校准的结构和方法
CN112782249B (zh) * 2020-12-28 2021-11-09 浙江大学 一种speek/il夹层结构参比电极及其制备方法和应用
EP4396569A1 (de) * 2021-08-31 2024-07-10 Virginia Commonwealth University Selbstkalibrierte elektrochemische sensoren
EP4170334A1 (de) 2021-10-21 2023-04-26 Vilnius University Enzymatischer selbstkalibrierender biosensor zur kontinuierlichen ph-überwachung
US11846598B2 (en) 2021-12-31 2023-12-19 Analog Devices International Unlimited Company Reference electrode
CN117825469B (zh) * 2024-02-29 2024-06-18 乐普（北京）医疗器械股份有限公司 一种Ag/AgCl参比电极组合物及Ag/AgCl参比电极和应用

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55135735A (en) * 1979-04-09 1980-10-22 Shimadzu Corp Reference electrode for potentiometry
JPH01136060A (ja) * 1987-11-24 1989-05-29 Terumo Corp 基準電極及びその製造方法
CA2267531A1 (en) * 1996-10-02 1998-04-09 Duke University Electrode for the electrochemical detection of nitric oxide
KR100342165B1 (ko) * 1999-03-25 2002-06-27 배병우 자기 진단기능을 갖는 소형 고체상 기준전극
WO2002090951A1 (en) * 2001-05-04 2002-11-14 Sensors For Medicine And Science, Inc. Electro-optical sensing device with reference channel
JP4117139B2 (ja) * 2002-03-07 2008-07-16 本田技研工業株式会社 フェロセン基含有ゲル化性有機化合物並びにそれを用いるゲル及びキャストフィルム
JP4024097B2 (ja) * 2002-07-12 2007-12-19 日華化学株式会社 参照電極及びこれを備える電解セル
AU2003262742A1 (en) * 2002-08-19 2004-03-03 Iowa State University Research Foundation, Inc. Redox polymer nanoparticles
JP4238716B2 (ja) * 2003-12-15 2009-03-18 富士ゼロックス株式会社 電気化学測定用電極及びその製造方法
GB2409902B (en) * 2004-01-08 2006-04-19 Schlumberger Holdings Electro-chemical sensor
JP2007526474A (ja) * 2004-03-04 2007-09-13 アイシス・イノベーション・リミテッド 電気化学センサー
JP3996629B2 (ja) * 2005-08-25 2007-10-24 松下電器産業株式会社 酸素還元用電極
GB2430749B (en) * 2005-09-21 2007-11-28 Schlumberger Holdings Electro-chemical sensor
JP2007095488A (ja) * 2005-09-29 2007-04-12 Toshiba Corp 発光素子およびその製造方法
EP2005161B1 (de) * 2006-03-17 2016-02-24 NewSouth Innovations Pty Limited Elektrochemischer sensor
JP5036003B2 (ja) * 2006-09-13 2012-09-26 国立大学法人京都大学 イオン液体被覆参照電極及びその参照電極を用いた電気化学測定装置
US8197650B2 (en) 2007-06-07 2012-06-12 Sensor Innovations, Inc. Silicon electrochemical sensors
US20090294284A1 (en) * 2008-05-28 2009-12-03 Chung Yuan Christian University Reference electrode
TWI502195B (zh) * 2009-03-10 2015-10-01 Senova Systems Inc 在用於測量樣品中之分析物的電化學感測裝置中所用的多相分析物非敏感性電極、包含此電極的電化學感測裝置，與使用此感測裝置測量樣品中之分析物的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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